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We have analyzed your query . You can customize the style of GroupHeader by creating style for CaptionSummaryRow. Please refer the below KB link to achieve your requirement.
KB Link: http://www.syncfusion.com/kb/4147/how-to-change-the-captionsummaryrow-style-based-on-the-grouping-level
You can also refer the below documentation link to know more about styling and customize the DataGrid parts,
Documentation Link: http://help.syncfusion.com/ug/wpf//Documents/stylesandtemplates2.htm
Please let us know if you need further assistance,
Thank you for your update. Please let us know if you need further assistance.